Polycyclic full quaternary nitrogen-heterocyclic phosphonates

ABSTRACT

Quaternary nitrogen-heterocyclic phosphonates wherein the phosphonate group is ortho- or para- to the nitrogen heterocyclic group, where the compounds are characterized as follows: ##STR1## wherein the dotted line represents a cyclic structure which cyclic structure may be the sole cyclic structure, or may be attached to other cyclic groups, where R is a hydrocarbon or a substituted hydrocarbon group such as alkyl, aryl, alkaryl, aralkyl, etc., and X is an anion such as halogen, a sulfite, a sulfate, a sulfonate-containing group, etc. 
     These nitrogen-heterocyclic phosphonates are prepared by reacting an aromatic nitrogen-heterocyclic compound, wherein the nitrogen atom is in the form of a quaternary alkoxy derivative (N--OR hereinafter defined) with a phosphite salt, preferably in the form of an ester of the phosphite, as exemplified by the following equation: ##STR2## Quaternaries of these compounds are prepared by further reaction with a quaternizing agent. 
     These compounds which may be characterized as quaternaries of phosphonates of nitrogen-heterocyclics have many uses including their use as biocides, such as bacteriocides, herbicides, corrosion inhibitors and chelating agents.

This is a continuation of Ser. No. 380,605, filed July 19, 1973, and nowabandoned, which in turn is a division of Ser. No. 117,082, filed Feb.19, 1971, now U.S. Pat. No. 3,770,750, patented Nov. 6, 1973.

This invention relates to quaternaries of nitrogen-heterocyclicphosphonates. More particularly this invention relates to quaternariesof nitrogen-heterocyclic phosphonates wherein the phosphonate group isortho or para to the heterocyclic nitrogen group. Still moreparticularly, this invention relates to compounds characterized by thefollowing groups: ##STR3## wherein the dotted lines indicate a cyclicstructure, which cyclic structure may be the sole cyclic structure ormay be attached to other cyclic groups. These compounds may becharacterized as phosphonates of quaternary nitrogen-heterocyclics.

This invention also relates to the preparation of these quaternaryphosphonates which comprises reacting an aromatic nitrogen-heterocyclic,wherein the nitrogen atom is in the form of a quaternary alkoxyderivative (N--OR), with a phosphite salt, preferably in the form of anester of the phosphite, as exemplified by the following equation:##STR4##

These products are then reacted with a quaternizing agent to yield thequaternaries of this invention as shown in the following equation:##STR5##

This invention also relates to uses for these quaternary compounds forexample as biocides, such as bacteriocides, herebicides, corrosioninhibitors, chelating agents, etc.

In my application Ser. No. 733,328 filed May 31, 1968, now abandoned,there are described and claimed processes for preparing dihydronitrogen-heterocyclic phosphonates and the resulting phosphonates whichare substituted ortho and/or para to the heterocyclic-nitrogen atom,etc. For example, the invention of Ser. No. 733,328 may be illustratedby the following equations: ##STR6## R₁, R₂, R₃, R₄, R₅, R₆ may behydrogen or a substituted group, for example, alkyl, cycloalkyl, aryl,alkaryl, aralkyl, etc.

R₇ is an ester moiety for example alkyl, aryl, cycloalkyl, aralkyl,alkaryl, etc., oxyalkylated groups, etc.

The groups of R₁ to R₇ may also be further substituted provided thesubstituted groups do not interfere with the reaction.

X is any suitable anion, for example, halogen, e.g., chlorine, bromine,iodine, etc., --SO₄ R", --SO₃ R" where R" is alkyl, etc., such as --SO₄Me, --SO₄ Et, ##STR7##

Application Ser. No. 801,856, filed Feb. 24, 1969, now U.S. Pat. No.3,673,196, relates to a process of preparing analogous nitrogenheterocyclic phosphonates as contrasted to the dihydro-heterocyclicphosphonates of Ser. No. 733,328 (i.e., full heterocyclic as contrastedto dihydro-heterocyclic).

The products of Ser. No. 801,856 may be illustrated by the followingequations: ##STR8## where R₁ is a hydrocarbon group such as alkyl,cycloalkyl, aryl, aralkyl, alkaryl, etc., R₂, R₃, R₄, R₅, R₆ is hydrogenor a substituted group, for example, alkyl, cycloalkyl, aryl, alkaryl,aralkyl, etc.

R₇ is an ester moiety for example alkyl, aryl, cycloalkyl, aralkyl,alkaryl, etc., oxyalkylated groups, etc.

The groups of R₁ to R₇ may also be further substituted provided thesubstituted groups do not interfere with the reaction.

X is any suitable anion, for example, halogen, e.g., chlorine, bromine,iodine, etc., --SO₄ R", --SO₃ R", where R" is alkyl, such as --SO₄ Me,--SO₄ Et, ##STR9##

It is to be noted that in the invention described in Ser. No. 733,328the R₁ group remains affixed to the heterocyclic nitrogen throughout thereaction and in the final product, thus yielding a dihydro derivative ofa heterocyclic compound; whereas in the present invention the nitrogenbonded OR₁ group is removed as an alcohol moiety during the reaction toyield the heterocyclic compound itself.

In preparing the compounds of Ser. No. 801,856 it is convenient to startwith nitrogen-heterocyclic compound, oxidize it to the N-oxide, reactthis with an alkyl ester of an inorganic acid such as alkyl halide,alkyl sulfate, etc., to form the OR₁ group, and to then react the saltof a phosphite ester to yield the heterocyclic phosphonate asillustrated by the following series of reactions: ##STR10##

Any nitrogen heterocyclic having an available ortho and/or para positioncapable of being activated by quaternary formation of the nitrogen groupwith an --OR₁ group so as to promote reaction with salts of phosphiteesters can be employed. This includes heterocyclics having one or morerings, where at least one ring has a nitrogen heterocyclic group and theother rings are carbocyclic or heterocyclic, i.e., they may containoxygen or other non-carbon elements in the ring, etc., for example,##STR11##

The above ring systems may also be substituted. The adjacent rings mayalso contain heterocyclic groups for example oxygen, nitrogen, etc.,and/or may contain rings having less than six molecules in the ring, forexample a 5 member ring.

In certain instances more than one nitrogen-heterocyclic ring may becapable of reacting with the phosphite salt so that phosphonatesubstitution may occur in more than one ring.

X is any suitable anion, for example, halogen, e.g., chlorine, bromine,iodine, etc., --SO₄ R", --SO₃ R" where R" is alkyl such as ##STR12##

Representative examples of heterocyclic reactants include pyridines andbenzo- and dibenzo- derivatives of pyridine, for example, pyridine,alkylated pyridines such as 2-picoline, 3-picoline, 4-picoline, etc.,2,4-lutidine, 2,6-lutidine, 2,3-lutidine, etc., collidines, etc.,quinoline and alkylated quinolines, etc., isoquinolines, and alkylatedisoquinolines, etc., phenanthridines, and substituted phenanthridines,etc., acridines and substituted acridines, etc.

The nitrogen group in the heterocyclic ring is reacted with aquaternizing agent to activate the ring.

The phosphorous-containing reactant is a metal salt of phosphorous acid,preferably in the form of an alkali metal salt in which the metal isdirectly bonded to phosphorous. In order to prevent undesirable sidereactions the phosphorous acid is used in the form of a derivative,preferably as a diester.

Where the phosphite ester contains more than one phosphite unit, aplurality of heterocyclic units may be joined thereto, for example##STR13##

In general, the reaction is carried out in an inert solvent which iswater free at a temperature and time sufficient to promote the desiredreaction. Ether solvents such as diethyl ether, dioxane andtetrahydrofuran are useful, as well as aromatic hydrocarbon solvent likebenzene, toluene, etc. Particularly useful are dipolar aprotic solventssuch as dimethyl sulfoxide, dimethyl formamide N-methyl pyrrolidone.Combinations of these various types of solvents can also beadvantageously used. Temperature and time are interrelated. Thus, atemperature of from 30° to the decomposition temperature of reactantsand products can be employed, the upper limit of temperature beinggenerally about 150° C., for a time of from 0.5-10 hours, but preferably1-3 hours. The inorganic salt is separated from the organic layer byfiltration or by water extraction and the phosphonate derivative isseparated from the organic layer. In addition the reaction is bestcarried out on an inert atmosphere such as nitrogen, argon, etc. In thisway the attack of oxygen on phosphite salts and on the products isprevented.

The following examples are presented by way of illustration and not oflimitation.

EXAMPLE 1 Diethyl Pyridine 2-phosphonate

To pyridine N-oxide (19 g; 0.2 mole) was added dimethyl sulfate (25.2 g;0.2 mole) during 30 minutes. The reaction was completed by heating at100° C. for two hours yielding N-methoxy pyridinium methosulfate.Diethyl sodio phosphonate was prepared by dissolving sodium (4.6 g; 0.2mole) in a solution of diethyl phosphite (27.6 g; 0.2 mole) in dioxane(100 ml) in an argon atmosphere. The N-methoxy pyridinium quaternary wassuspended in toluene by stirring while the diethyl sodio phosphonatesolution was added. The reaction flask was cooled to maintain thetemperature at 25°-35° C. After stirring for 11/2 hours, water (100 ml)was added and the organic product isolated by chloroform extraction.Evaporation of the chloroform extract and distillation yielded diethylpyridine-2-phosphonate with a small amount of diethyl pyridine4-phosphonate. Yield -- 14g (33%) bp 140°-8° C./1.5 mm. The presence ofthe two isomers was established by infrared absorption; 2-isomer 13.3 μ(strong, 4 adjacent hydrogen) and 4 isomer, 12.3 μ (weak, 2 adjacenthydrogen).

EXAMPLE 2 Diethyl 4-methyl Pyridine-2-Phosphonate

N-methoxy-4-methyl pyridinium methosulfate was prepared from4-picoline-N-oxide (54.4g; 0.5 mole) and dimethyl sulfate (63g; 0.5mole) and suspended by stirring with toluene (250 ml). To thissuspension was added diethyl sodio phosphonate in dioxane (150 ml)prepared from diethyl phosphite (69g; 0.5 mole) and sodium (11.5g; 0.5mole). This addition was carried out in 40 minutes during which time thetemperature was controlled at 45° C. by cooling. After stirring for onehour, water was added to the reaction and the product isolated bychloroform extraction. Evaporation and distillation yielded diethyl4-methyl pyridine-2-phosphonate 17g; bp 109°-112° 0.05 mm. The infraredspectrum shows absorption at 7.97 μ (P═O), 9.8 μ and 10.4 μ (P--O--C).

EXAMPLE 3 Diethyl Quinoline-2-Phosphonate and -4-Phosphonate

N-methoxyquinolinium methosulfate was prepared from quinoline N-oxide(50g; 0.344 mole) and dimethyl sulfate (43.5g; 0.344 mole). To thisquaternary was added diethyl sodiophosphonate from diethyl phosphite(47.5g; 0.344 mole) and sodium (7.9g; 0.344 mole) in dioxane (100 ml.).The reaction was completed by heating at 100°-110° C. for two hours.Water was added to the reaction, after cooling, and the product wasisolated by benzene extraction. Evaporation of the solvent and heatingunder vacuum at 140° C./2 mm gave a residue which was a mixture ofdiethyl quinoline 2-phosphonate and 4-phosphonate. Analysis found N =5.4% calculated N. 5.28%.

EXAMPLE 4 Diethyl Isoquinoline-1-Phosphonate

N-methoxy isoquinolinium methosulfate was converted by reaction withdiethyl sodio phosphonate in dioxane into diethylisoquinoline-1-phosphonate in 30% yield using the procedure of Example3. The product was purified by distillation bp 135°-140° C./0.15 mm.

EXAMPLE 5 Diethyl 4-Cyanopyridine-2-Phosphonate

4-cyano pyridine N-oxide was converted into its N-methoxy pyridiniumsalt with dimethyl sulfate and reacted in dioxane with diethyl sodiophosphonate by heating at 80°-85° C. for one hour. After cooling, waterwas added and the product isolated by chloroform extraction. Removal ofunreacted reactants under vacuum left the slightly impure diethyl4-cyano pyridine-2-phosphonate (70%). The infrared spectrum showedabsorption at 4.5 μ (C.tbd.N), 7.95 μ (P═O), 9.8 μ (P--O--C).

EXAMPLE 6 4-Methyl Pyridine-2-Phosphonic Acid

Diethyl 4-methyl pyridine-2-phosphonate (11g.). (The product fromExample 2) was heated for six hours with 18% hydrochloric acid (120 ml)at 100°. The acid was removed under vacuum to leave a gum which wasdissolved in ethyl alcohol. Addition of ether yielded white crystalswhich after drying gave pure 4-methyl pyridine 2-phosphonic acid (7.2g;86) mp 272.6° C.

Analysis calculated: C, 41.62; H, 5.78; N, 8.09; P, 17.92%. Found: C,41.65; H, 4.63; H, 8.09; P, 16.95%.

EXAMPLE 7 Quinoline 2- and -4-Phosphonic Acids

The product of Example 3 (7.7g) was heated under reflux for 31/2 hourswith 18% hydrochloric acid (60 ml.). Using the isolation procedure ofExample 6 a crude quinoline phosphonic acid 5g. (82%) was isolated.Crystallization from acetic acid gave pure quinoline-2-phosphonic acidmp 200° C.

Analysis Calculated: N, 6.70%; P, 14.83%. Found: N, 6.33%; P, 14.71%.

With the above examples as illustrative examples, one can then react anyof the nitrogen-heterocyclic phosphonates of Ser. No. 801,856 to yieldthe corresponding quaternaries. The resulting compounds will correspondto those of Ser. No. 801,856 except that the cyclic nitrogen isquaternized.

Thus, the ring will contain the following group ##STR14## the rest ofthe molecule being unchanged.

Thus, the present invention relates to the reaction of thenitrogen-heterocyclic phosphates of Ser. No. 801,856 with quaternizingagents to form the corresponding quaternary compounds.

In general these quaternaries are prepared by carrying out the reactionunder suitable conditions. For example, the nitrogen-heterocyclicphosphate either per se or dissolved in a suitable solvent and at leasta stoichiometric amount of the quaternizing agent are mixed and thereaction mixture heated at a temperature and time sufficient to yieldthe quaternary product, for example, at about 60° C. to thedecomposition point of reactants and products, such as from about 60° to175° C. or higher, for example from about 80° to 150° C. for a period offrom about one to 24 hours, such as from about 3 to 10 hours, butpreferably about 4 to 6 hours. A convenient method of reaction is todissolve the reactants in a suitable solvent and heat a reflux untilquaternization is effected.

The following examples are presented by way of illustration.

EXAMPLE 1 Diethyl Pyridine-2 phosphonate Methoiodide

Diethyl pyridine-2-phosphonate (2g) was heated under reflux with methyliodide (4.5g) in ethanol (20 ml) for 4 hours. Evaporation of the solventand excess methyl iodide gave the pyridinium methiodide as a colorlessoil which was readily water soluble. The structure of the product is:##STR15##

EXAMPLE 2 Diethyl Pyridine-2-Phosphonate Methyl Quaternary Methosulfate

Diethyl pyridine-2-phosphonate (4.3g) was heated under reflux in ethanol(30 ml) with dimethyl sulfate (2.5g) for 5 hours. Removal of solventyielded the pure quaternary as an oil represented by the structure:##STR16##

EXAMPLE 3 N-propyl Quaternary of Diethyl Pyridine-2-phosphonate

Diethyl pyridine-2-phosphonate (4.3g) was heated under reflux in ethanol(30 ml) with N-propyl iodide (3.6g) for 5 hours. Evaporation of thesolvent gave the N-propyl-quaternary iodide as an oil represented asfollows: ##STR17##

EXAMPLE 4 Quaternary from 1-Bromododecane and DiethylPyridine-2-Phosphonate

Diethyl pyridine-2-phosphonate (4g) and 1-bromododecane (4.65g) wereheated at 140°-150° for 6 hours without solvent to effectquaternization. The product is represented as follows: ##STR18##

Other nitrogen-heterocyclic phosphonates prepared in Ser. No. 801,856are similarly quaternized.

In order to save repetitive detail, the results are presented in tabularform:

    __________________________________________________________________________       Nitrogen                                                                      Heterocyclic     Quaternizing                                                                         Quaternary                                         Ex.                                                                              Phosphonate      Agent  Product                                            __________________________________________________________________________        ##STR19##       (C.sub.2 H.sub.5 O).sub.2 SO.sub.2                                                    ##STR20##                                             ##STR21##       CH.sub.3 I                                                                            ##STR22##                                             ##STR23##       CH.sub.3 I                                                                            ##STR24##                                             ##STR25##       (CH.sub.3 O).sub.2 SO.sub.2                                                           ##STR26##                                             ##STR27##       C.sub.12 H.sub.25 Br                                                                  ##STR28##                                         10.                                                                               ##STR29##       C.sub.12 H.sub.25 Br                                                                  ##STR30##                                             ##STR31##       C.sub.12 H.sub.25 Br                                                                  ##STR32##                                         __________________________________________________________________________

where the phosphite ester contains more than one heterocyclic unit,corresponding polyquaternaries will be formed, for example, ##STR33##

In addition, mono-heterocyclics can be reacted with polyquaternizingagent as a diquaternizing agent to yield diquaternaries, for example:##STR34## where R' is for example alkylene, cycloalkylene, arylene,alkarylenealkyl, dialkylether, alkenylene, alkynylene, etc., for examplewhere R' is

    ______________________________________                                        (CH.sub.2)       or branched derivatives thereof,                             1-10             or substituted derivatives thereof,                           ##STR35##       or substituted derivatives thereof,                           ##STR36##       or substituted derivatives thereof,                           ##STR37##       or substituted derivatives thereof,                          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2,                                         CH.sub.2 CHCHCH.sub.2                                                         CH.sub.2 CCCH.sub.2, etc.                                                     ______________________________________                                    

Corresponding diquaternaries of other heterocyclics can also beprepared, for example, ##STR38##

As is quite evident, other quaternary nitrogen-heterocyclic phosphonatesare useful in my invention. It is, therefore, not only impossible toattempt a comprehensive catalogue of such compounds, but to attempt todescribe the invention in its broader aspects in terms of specificquaternary nitrogen-heterocyclic phosphonates would be too voluminousand unnecessary since one skilled in the art could by following thedescription of the invention herein select a useful quaternary. Thisinvention lies in the reaction of suitable quaternaries and theirindividual compositions are important only in the sense that they reactto form useful products. To precisely define each specific usefulquaternary in light of the present disclosure would merely call forchemical knowledge within the skill of the art in a manner analogous toa mechanical engineer who prescribes in the construction of a machinethe proper materials and the proper dimensions thereof. From thedescription in this specification and with the knowledge of a chemist,one will know or deduce with confidence the applicability of specificquaternaries suitable for this invention. In analogy to the case of amachine, wherein the use of certain materials of construction ordimensions of parts would lead to no practical useful result, variousmaterials will be rejected as inapplicable where others would beoperative. I can obviously assume that no one will wish to use a uselessquaternary nor will be misled because it is possible to misapply theteachings of the present disclosure to do so. Similarly, any quaternarynitrogen-heterocyclic phosphonate which is within the scope of thisinvention and effective as a biocide (as hereinafter stated) is withinthe scope of this invention.

I. WATER TREATMENT

This phase of the present invention relates to the treatment of water.More particularly, it is directed to providing improved means forcontrolling microbiological organisms including bacteria, fungi, algae,protozoa and other microbiological organisms which, if uncontrolled,multiply under certain conditions so as to present many seriousproblems. For example, in swimming pools the growth of thesemicrobiological organisms is very desirable from a sanitary standpointas well as for general appearances and maintenance. In industrial watersystems such as cooling towers, condenser boxes, spray condensers, watertanks, basins, gravel water filters, and the like, microbiologicalorganisms may interfere greatly with proper functioning of equipment andresult in poor heat transfer, clogging of systems and rotting of woodenequipment, as well as many other costly and deleterious effects.

In other industrial applications where water is used in processes, asfor example, as a carrying medium, etc., microbiological organisms mayalso constitute a problem in maintenance and operation. Illustrative ofsuch industrial applications are the pulp and paper manufacturingprocesses, oil well flooding operations and the like.

The products of this invention are suitable as biocides for industrial,agricultural and horticultural, military, hygienic and recreationalwater supplies. They provide an inexpensive, easily prepared group ofproducts which can be used, in minimal amounts, in water supplies, incooling towers, air-conditioning systems, on the farm and ranch, in thefactory, in civilian and military hospitals and dispensaries, in camps,for swimming pools, baths and aquaria, waterworks, wells, reservoirs, byfire-fighting agencies, on maritime and naval vessels, in boilers,steam-generators and locomotives, in pulp and paper mills, forirrigation and drainage, for sewage and waste disposal, in the textileindustry, in the chemical industries, in the tanning industry, etcetera, and which will render said water supplies bactericidal,fungicidal and algicidal. They further provide a simple process wherebywater supplies, for whatever purposes intended, are renderedbacteriostatic, fungistatic and algistatic, i.e., said water suppliestreated by the process of this invention will resist and inhibit thefurther growth or proliferation of bacteria, fungi, algae and all formsof microbial life therein.

II. WATER FLOODING IN SECONDARY RECOVERY OF OIL

This phase of the present invention relates to secondary recovery of oilby water flooding operations and is more particularly concerned with animproved process for treating flood water and oil recovery therewith.More particularly this invention relates to a process of inhibitingbacterial growth in the recovery of oil from oil-bearing strata by meansof water flooding takes place in the presence of sulfate-reducingbacteria.

Water flooding is widely used in the petroleum industry to effectsecondary recovery of oil. By employing this process the yield of oilfrom a given field may be increased beyond the 20 - 30 percent of theoil in a producing formation that is usually recovered in the primaryprocess. In flooding operations, water is forced under pressure throughinjection wells into or under oil-bearing formations to displace the oiltherefrom to adjacent producing wells. The oil-water mixture is usuallypumped from the producing wells into a receiving tank where the water,separated from the oil, is siphoned off, and the oil then transferred tostorage tanks. It is desirable in carrying out this process to maintaina high rate of water injection with a minimum expenditure of energy. Anyimpediment to the free entry of water into oil bearing formationsseriously reduces the efficiency of the recovery operation.

The term "flood water" as herein employed is any water injected intooil-bearing formations for the secondary recovery of oil. Inconventional operations, the water employed varies from relatively purespring water to brine and is inclusive of water reclaimed from secondaryrecovery operations and processed for recycling. The problems arisingfrom the water employed depend in part on the water used. However,particularly troublesome and common to all types of water are problemsdirectly or indirectly concerned with the presence of microorganisms,such as bacteria, fungi and algae. Microorganisms may impede the freeentry of water into oil-bearing formations by producing ions susceptibleof forming precipitates, forming slime and/or existing in sufficientlyhigh numbers to constitute an appreciable mass, thereby plugging thepores of the oil-bearing formation. Pore-plugging increases the pressurenecessary to drive a given volume of water into an oil-bearing formationand oftentimes causes the flooding water to by-pass the formation to beflooded. In addition, microorganisms may bring about corrosion by actingon the metal structures of the wells involved, producing corrosivesubstances such as hydrogen sulfide, or producing conditions favorableto destructive corrosion such as decreasing the pH or producing oxygen.The products formed as the result of corrosive action may also bepore-plugging precipitates. Usually, the difficulties encountered are acombination of effects resulting from the activity of differentmicroorganisms.

Organisms of the Desulfovibrio genus, more commonly known as sulfatereducing bacteria, are known particularly to preclude efficientoperation of oil recovery by conventional water flooding techniques byproducing H₂ S which reacts with iron or iron salts to precipitate blackferrous sulfide. These organisms are resistant to the effects of manyknown antimicrobial compounds.

III. HYDROCARBON TREATMENT

This phase of the present invention relates to the use of quaternariesas biocides in hydrocarbon systems.

In addition to being used as biocides in aqueous systems, the quaternarycompounds of this invention can also be employed as biocides inhydrocarbon systems, particularly when petroleum products are stored. Itis believed that bacteria and other organisms, which are introduced intohydrocarbon systems by water, feed readily on hydrocarbons resulting ina loss in product; that microorganisms cause the formation of gums, H₂S, peroxides, acids and slimes at the interface between water and oil;that bacterial action is often more pronounced with rolling motion thanunder static conditions, etc. Loss of product, corrosion of the storagetank, clogging of filters and metering instruments, and fueldeterioration are among the harmful effects of bacteria growth in fuels.The activity of microorganism growth is often increased by the presenceof rust. Not only do these microorganisms often encourage rust but rustencourages microorganism growth. Since microorganism growth appears tobe considerably higher with kerosene than with gasoline, plugged filtersexperienced with jet fuels which contain large amounts of kerosene is aserious problem.

IV. MICROBIOCIDAL TESTING

The procedure was carried out in the following manner. Solutions of testcompounds were aseptically added to a sterile broth which would supportgrowth of the following test organisms

(1) Aerobic bacteria

(2) Sulfate reducing bacteria

to a concentration of 500 ppm by weight of broth. Growth mediaprescribed by the American Petroleum Institute were used. The brothcontaining the test compound was then dispersed into sterile disposabletubes and the tubes were innoculated with the growing organisms andincubated at 35° C. for 24 hours. The absence or presence of growth ofmicroorganisms was determined by visual inspection with the followingtest compounds.

    ______________________________________                                        Ex. 2                                                                                       ##STR39##                                                       Ex. 3                                                                                       ##STR40##                                                       Ex. 4                                                                                       ##STR41##                                                   

In contrast to the corresponding unquaternized compounds which showed noactivity, the above compounds were active as biocides or biostats.

Having thus described my invention, what I claim is new and desire to obtain by Letters Patent is:
 1. A full quaternary nitrogen-heterocyclic phosphonate selected from the group consisting of ##STR42## where R and R₇ are each alkyl and X is an anion.
 2. The full quaternary nitrogen-heterocyclic phosphonate compound of claim 1 having formula (1).
 3. The full quaternary nitrogen-heterocyclic phosphonate compound of claim 1 having the formula (3).
 4. The full quaternary nitrogen-heterocyclic phosphonate of claim 1 which is the mixture (2).
 5. The full quaternary nitrogen-heterocyclic phosphonate of claim 1 where X is selected from the group consisting of chlorine, bromine, iodine, --SO₄ R" and --SO₃ R", where R" is alkyl.
 6. The full quaternary nitrogen-heterocyclic phosphonate compound of claim 1 having the formula ##STR43##
 7. The full quaternary nitrogen-heterocyclic phosphonate of claim 1 having the formula ##STR44## 